Bisimino-substituted phenyl compounds and their use as pesticides

ABSTRACT

Bisimino-substituted phenyl compounds of the formula I                    
     where the substituents have the following meanings: 
     X is a group A or B                    
      where 
     # denotes the bond with the phenyl ring and 
     R a  is halogen, alkyl or alkoxy; 
     Y is halogen, alkyl, haloalkyl or alkoxy; 
     n is 0, 1 or 2, it being possible for the radicals Y to be different if n=2; 
     R 1  is alkyl; 
     R 2  is alkyl, haloalkyl, alkenyl, haloalkenyl, alkynyl or haloalkynyl; 
     R 3  is hydrogen, alkyl, haloalkyl or substituted or unsubstituted phenyl; 
     R 4  is ═CR b R c  or ═N—OR d  where 
     R b , R c  independently of one another are hydrogen, alkyl or substituted or unsubstituted phenyl; and 
     R d  is one of the radicals mentioned under R 2 . 
     Processes and intermediates for their preparation, and their use.

The present invention relates to a bisimino-substituted phenyl compoundof the formula I

where the substituents have the following meanings:

X is a group A or B

 where

# denotes the bond with the phenyl ring and

R^(a) is halogen, C₁-C₄-alkyl or C₁-C₄-alkoxy;

Y is halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl or C₁-C₄-alkoxy;

n is 0, 1 or 2, it being possible for the radicals Y to be different ifn=2;

R¹ is C₁-C₄-alkyl;

R² is C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₃-C₄-alkenyl, C₃-C₄-haloalkenyl,C₃-C₄-alkynyl or C₃-C₄-haloalkynyl;

R³ is hydrogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl or substituted orunsubstituted phenyl;

R⁴ is ═CR^(b)R^(c) or ═N—OR^(d) where

R^(b), R^(c) independently of one another are hydrogen, C₁-C₆-alkyl orsubstituted or unsubstituted phenyl; and

R^(d) is one of the radicals mentioned under R².

In addition, the invention relates to processes and intermediates forthe preparation of the compounds I, and to compositions and to the useof the compounds I for controlling harmful fungi and animal pests.

WO-A 97/02,255 discloses 4-phenyl-2,3-dihydroisoxazolones and4-phenyl-2,4-dihydrotriazolones with a methoxyimino group in theortho-position.

WO-A 95/21,153 and WO-A 97/05,103 describeα-phenylacrylic acid andα-phenyl-α-methoxyiminoacetic acid derivatives with a bisoxime ethergroup in the ortho-position, and PCT/EP 96/04,446 describes suchderivatives which have a trisoxime ether group.

The compounds described in the documents mentioned above are suitable ascrop protection agents against harmful fungi and, in some cases, againstanimal pests.

However, their action is not satisfactory in many cases. It is an objectof the invention to provide compounds with an improved activity.

We have found that this object is achieved by the phenyl compounds ofthe formula I. We have furthermore found intermediates and processes forthe preparation of the compounds I, and the use of the compounds I andof compositions comprising them for controlling harmful fungi and animalpests. The fungicidal action is preferred.

The compounds of the formula I differ from the compounds disclosed inthe above document WO-A 97/02,255 in as far as the oximino group issubstituted by a radical R⁴ which is bonded to a double bond and whichcannot be hydrogen. Compared with the known compounds, the compounds ofthe formula I have a better activity against harmful fungi and animalpests.

In principle, the compounds of the formula I can be obtained usingsimilar methods to those described in WO-A 97/02,255, WO-A 95/21,153 andWO-A 97/05,103 and in PCT/EP 96/04,446.

The compounds I can be obtained by various routes, it being immaterialfor the synthesis whether it is the group X or the oxime ether groupwhich is synthesized first. In the descriptions of the reactions whichfollow, therefore, the term X^(#) will be used for the radical X or asuitable precursor of this radical and E^(#) for the oxime ether groupor a suitable precursor, for reasons of better readability.

In particular, compounds of the formula I.1

are obtained by converting a benzyl compound of the formula II^(#) withan oxime of the formula III and converting the resulting oxime ether ofthe formula IV^(#) into the halogen compound of the formula V^(#) bymeans of halogenation, reacting V^(#) with a hydroxylamine ether of theformula VI′ to give the bisoxime of the formula VI^(#), oxidizing VI^(#)to give the carbonyl compound of the formula VII^(#), and reactingVII^(#) with a phosphorus reagent following the principles of Wittigreaction to give a compound of the formula I.1^(#).

In formula II^(#), L is a nucleophilically exchangeable group, forexample halogen, such as fluorine, chlorine, bromine or iodine, inparticular chlorine or bromine, or alkyl- or arylsulfonates, such asmesylate or tosylate.

In the above equation, {circle around (P)} in formula VII′ is aphosphoranyl dical such as, for example, triphenylphosphoranyl.

1. The reaction of the benzyl compound II^(#) with the oxime of theformula III^(#) is carried out in a manner known per se at from −10° C.to 100° C., preferably 10° C. to 85° C., in an inert organic solvent inthe presence of a base [cf. WO-A 97/02,255; WO-A 96/36,229].

 Suitable solvents are ethers such as diethyl ether, diisopropyl ether,tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran, nitrilessuch as acetonitrile and propionitrile, ketones such as acetone, methylethyl ketone, diethyl ketone and tert-butyl methyl ketone, alcohols suchas methanol, ethanol, n-propanol, isopropanol, n-butanol andtert-butanol, and also dimethyl sulfoxide, dimethylformamide anddimethylacetamide, particularly preferably tetrahydro-furan,acetonitrile and dimethylformamide. Mixtures of the solvents mentionedmay also be used.

 Suitable bases are, generally, inorganic compounds such as alkali metalhydroxides and alkaline earth metal hydroxides such as lithiumhydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide,alkali metal hydrides and alkaline earth metal hydrides such as lithiumhydride, sodium hydride, potassium hydride and calcium hydride, alkalimetal carbonates and alkaline earth metal carbonates such as lithiumcarbonate, potassium carbonate and calcium carbonate, and also alkalimetal hydrogen carbonates such as sodium hydrogen carbonate, alkalimetal alkoxides and alkaline earth metal alkoxides such as sodiummethoxide, sodium ethoxide, potassium ethoxide, potassium tert-butoxideand dimethoxy-magnesium, furthermore organic bases, eg., tertiary aminessuch as trimethylamine, triethylamine, triisopropylethyl-amine andN-methylpiperidine, pyridine, substituted pyridines such as collidine,lutidine and 4-dimethylaminopyridine, and also bicyclic amines.Particularly preferred are sodium hydride, potassium carbonate andsodium methoxide.

 The bases are generally employed in catalytic amounts, but they mayalso be used in equimolar amounts, in an excess or, if appropriate, asthe solvent.

 The starting materials are generally reacted with each other inequimolar amounts. It may be advantageous for the yield to employ III inan excess based on II^(#).

 The benzyl compounds II^(#) which are required for the preparation ofthe compounds I are disclosed in the literature [cf. WO-A 97/02,255].They can be obtained by the following synthesis route:

 Compounds of the formula IIA^(#) where R^(a) is alkyl are obtained inthe manner disclosed in U.S. Pat. No. 4,952,573 from correspondingphenylacetic acid esters IIc^(#).

 This route is not only suitable for the preparation of the benzylcompounds II^(#), but, in principle, suitable for synthesizing thegroups A or B at each synthesis level of the oxime ether group E^(#).The group X is particularly preferably synthesized at the level of thecompounds IIa or IIe where E^(#) is hydrogen.

 The benzyl compounds IIB^(#) required for the preparation of thecompounds IB where R^(a) is alkyl which are not known from theliterature [cf. WO-A 96/36229] can be obtained using methods similar tothose of the literature [cf. J. Org. Chem., Vol. 43 (1978), p. 936].They can be obtained by reacting the carbamates of the formula IIf^(#)with orthoesters:

 Those oximes of the formula III which are not already known from theliterture [cf. EP-A 95/21,153] can be prepared in accordance with theliterature cited.

2. Halogenation of the oxime ether IV^(#) is usually carried out at from−10° C. to 80° C., preferably 0° C. to 65° C., in an inert organicsolvent in the presence or absence of an acid. J. Org. Chem. (1981), p.2532; Org, Synth., Vol. 55 (1976), p. 24; Tetrahedron (1970) p. 5611].

 Suitable halogenating agents are bromine, chlorine, pyridin*HBr₃, CuBr₂and SO₂Cl₂, in particular bromine, CuBr₂ and SO₂Cl₂. They are generallyreacted with each other in equimolar amounts. It may be advantageous forthe yield to employ them in a 1.2- to 2.5-fold excess based on thecompound IV^(#).

 Suitable solvents are aromatic hydrocarbons such as toluene, o-, m- andp-xylene, halogenated hydrocarbons such as methylene chloride,chloroform and chlorobenzene, and also alcohols such as methanol,ethanol, n-propanol, isopropanol, n-butanol and tert-butanol,particularly preferably cyclohexane, methylene chloride, chloroform,chlorobenzene and methanol. Mixtures of these may also be used.

 Acids and acidic catalysts which are used are inorganic acids such ashydrochloric acid, hydrobromic acid and sulfuric acid, Lewis acids suchas boron trifluoride, aluminum trichloride, iron(III) chloride, tin(IV)chloride, titanium(IV) chloride and zinc(II) chloride, and organic acidssuch as formic acid, acetic acid, propionic acid, oxalic acid, citricacid and trifluoroacetic acid.

 The acids are generally employed in catalytic amounts, but they canalso be used in equimolar amounts, in an excess or, if appropriate, asthe solvent.

 The starting materials are generally reacted with each other inequimolar amounts. It may be advantageous for the yield to employ thehalogenating agent in an excess based on IV^(#).

3. The reaction of the oxime ether V^(#) with the hydroxylamine ether ofthe formula VI′ to give the bisoxime ether VI^(#) is carried out in aknown manner at from 0° C. to 85° C., preferably at from 20° C. to 65°C., in an inert organic solvent.

4. The oxidation of the bisoxime ether VI^(#) is carried out in a knownmanner at from 20° C. to 160° C., preferably at from 20° C. to 100° C.,in an inert organic solvent, in the presence or absence of a base [cf.Houben-Weyl, Methoden der organischen Chemie [Methods in organicchemistry], Volume E3, pp. 247-265, Georg Thieme Verlag, Stuttgart1983].

 Examples of suitable oxidants are N-methylmorpholine N-oxide,2-benzoyl-1-trifluoromethanesulfonylhydrazine, trimethylamine N-oxideand pyridine N-oxide, in particular N-methylmorpholine N-oxide,trimethylamine N-oxide and pyridine N-oxide.

 Suitable bases are, generally, inorganic compounds such as alkali metalhydroxides and alkaline earth metal hydroxides such as lithiumhydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide,alkali metal carbonates and alkaline earth metal carbonates such aslithium carbonate, potassium carbonate and calcium carbonate, and alsoalkali metal hydrogen carbonates such as sodium hydrogen carbonate,moreover organic bases, eg. tertiary amines such as trimethylamine,triethylamine, triisopropylethylamine and N-methylpiperidine, pyridine,substituted pyridines such as collidine, lutidine and4-dimethylaminopyridine, and also bicyclic amines. Particularlypreferred are sodium hydroxide, sodium hydrogen carbonate and potassiumcarbonate.

 The bases are generally employed in catalytic amounts, but they canalso be used in equimolar amounts, in an excess or, if appropriate, asthe solvent.

 The starting materials are generally reacted with each other inequimolar amounts. It may be advantageous for the yield to employ theoxidant in an excess based on VI^(#).

5. The Wittig reaction is carried out in a known manner at from −78° C.to 85° C., preferably −10° C. to 65° C., in an inert organic solvent inthe presence of a base [cf. EP-A 513 580].

 The reaction mixtures are worked up in the customary manner, eg. bymixing with water, separating the phases and, if appropriate, purifyingthe crude products by chromatography. Some of the intermediates and endproducts are obtained in the form of colorless or pale brown viscousoils which are purified or freed from volatile components under reducedpressure and at a moderately elevated temperature. If the intermediatesand end products are obtained as solids, they may also be purified byrecrystallization or digestion. Those starting materials of the formulaIII required for the preparation of the compounds I which are notalready known from the literature [J. Org. Chem. (1991), p. 2605; Bull.Soc. Chim. Fr. (1973), p. 1452] can be prepared in accordance with theliterature cited.

Compounds of the formula I.2 are obtained for example by reacting acarbonyl compound of the formula VI^(#) with a hydroxylamine ether ofthe formula VIII^(#).

6. The reaction of the carbonyl compound VI^(#) to give the trioximeether I.2^(#) is normally carried out at from 10° C. to 120° C.,preferably 20° C. to 85° C., in an inert organic solvent in the presenceor absence of a base [cf. EP-A 386 561].

 Suitable solvents are ethers such as diethyl ether, diisopropyl ether,tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran, nitrilessuch as acetonitrile and propionitrile, alcohols such as methanol,ethanol, n-propanol, isopropanol, n-butanol and tert-butanol, and alsodimethylsulfoxide, dimethylformamide and dimethylacetamide, especiallypreferably methanol and ethanol. Mixtures of these may also be used.

 Bases which are suitable are, generally, inorganic compounds such asalkali metal carbonates and alkaline earth metal carbonates such aslithium carbonate, potassium carbonate and calcium carbonate, and alsoalkali metal hydrogen carbonates such as sodium hydrogen carbonate,alkali metal alkoxides and alkaline earth metal alkoxides such as sodiummethoxide, sodium ethoxide, potassium ethoxide, potassium tert-butoxideand dimethoxymagnesium, moreover organic bases, eg. tertiary amines suchas trimethylamine, triethylamine, triisopropyl-ethylamine andN-methylpiperidine, pyridine, substituted pyridines such as collidine,lutidine and 4-dimethylamino-pyridine and bicyclic amines. Especiallypreferred are sodium hydrogen carbonate, pyridine and triethylamine.

 The bases are generally employed in catalytic amounts, but they canalso be used in equimolar amounts, in an excess or, if appropriate, asthe solvent.

 The starting materials are generally reacted with each other inequimolar amounts. It may be advantageous for the yield to employ VIIIin an excess based on VI^(#).

The reaction mixtures are worked up in the customary manner, eg. bymixing with water, separating the phases and, if appropriate, purifyingthe crude products by chromatography. Some of the intermediates and endproducts are obtained in the form of colorless or pale brown viscousoils which are purified or freed from volatile components under reducedpressure and at a moderately elevated temperature. If the intermediatesand end products are obtained as solids, they may also be purified byrecrystallization or digestion.

Due to the C═C and C═N double bonds of the compounds I, theirpreparation may yield E/Z isomer mixtures which may be separated intothe individual compounds in the customary manner, for example bycrystallization or chromatography.

If the synthesis yields isomer mixtures, however, separation isgenerally not absolutely necessary since in some cases the individualisomers can be converted into each other during processing for use orupon use (eg. when exposed to light, acids or bases). Such conversionsmay also take place after use, for example when plants are treated inthe treated plant or in the harmful fungus or animal pest to becontrolled.

As regards the —N═CR¹—C(CR³R⁴)═NOR² double bonds, the E,E-isomers of thecompounds I are generally preferred with a view to their activity(configuration based on the radical —CH₂O— relative to the—C(CR³R⁴)═NOR² group, or based on the radical —OR² relative to the—C(R¹)—N═OCH₂ group).

In the definitions of the symbols given for the above formulae,collective terms were used which generally represent the followingsubstituents:

halogen: fluorine, chlorine, bromine and iodine;

alkyl: saturated straight-chain or branched hydrocarbon radicals having1 to 4 or 6 carbon atoms, eg. C₁-C₆-alkyl such as methyl, ethyl, propyl,1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl,pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl,1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl,1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl,1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl,2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl,2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl,1-ethyl-1-methylpropyl and 1-ethyl-2-methylpropyl;

haloalkyl: straight-chain or branched alkyl groups having 1 to 4 carbonatoms (as mentioned above), it being possible for some or all of thehydrogen atoms in these groups to be replaced by halogen atoms asmentioned above, eg. C₁-C₂-haloalkyl such as chloromethyl, bromomethyl,dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl,trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl,chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl,2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl,2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl,2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl and pentafluoroethyl;

alkoxy: straight-chain or branched alkyl groups having 1 to 4 carbonatoms (as mentioned above) which are bonded to the skeleton via anoxygen atom (—O—);

alkenyl: unsaturated straight-chain or branched hydrocarbon radicalshaving 3 to 4 carbon atoms and a double bond in any position, eg.C₃-C₄-alkenyl such as 1-propenyl, 2-propenyl, 1-methylethenyl,1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl,2-methyl-1-propenyl, 1-methyl-2-propenyl and 2-methyl-2-propenyl;

haloalkenyl: unsaturated straight-chain or branched hydrocarbon radicalshaving 3 to 4 carbon atoms and a double bond in any position (asmentioned above), it being possible for some or all of the hydrogenatoms in these groups to be replaced by halogen atoms as mentionedabove, in particular fluorine, chlorine and bromine;

alkynyl: straight-chain or branched hydrocarbon groups having 3 to 4carbon atoms and a triple bond in any position, eg. C₃-C₄-alkynyl suchas ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl and1-methyl-2-propynyl;

haloalkynyl: unsaturated straight-chain or branched hydrocarbon radicalshaving 3 to 4 carbon atoms and a triple bond in any position (asmentioned above), it being possible for some or all of the hydrogenatoms in these groups to be replaced by halogen atoms as mentionedabove, in particular fluorine, chlorine and bromine;

The addition “substituted or unsubstituted”, when referring to thephenyl radical, is intended to express that this radical can bepartially or fully halogenated [ie. some or all of the hydrogen atoms ofthis radical can be replaced by identical or different halogen atoms asmentioned above (preferably fluorine, chlorine or bromine, in particularfluorine or chlorine)] and/or can have attached to them one to four (inparticular one to three) of the following radicals:

halogen, cyano, nitro, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy,C₁-C₄-haloalkoxy, C₁-C₄-alkylamino, di-C₁-C₄-alkylamino andC₁-C₄-alkylthio.

Especially preferred with a view to their intended use are thosecompounds of the formula I where R^(a) is C₁-C₂-alkyl or C₁-C₂-alkoxy.

Especially preferred are compounds of the formula IB.

Equally preferred are compounds of the formula I where n=zero (0).

Particularly preferred compounds of the formula I are those where R^(a)is methyl or methoxy.

Besides these, preferred compounds are those of the formula I.1.

Equally preferred are compounds I.1 where R^(b) is hydrogen.

Furthermore preferred are compounds of the formula I.2.

Particularly preferred compounds I.1 are those where R³ and Y_(n) arehydrogen and R² is methyl or ethyl.

In addition, especially preferred compounds I.1 are those where R³ ishydrogen, R² is methyl or ethyl and Y_(n) is 6-methyl.

Equally, especially preferred compounds I.2 are those where R¹ and R³are methyl, Y_(n) is hydrogen and R² is methyl or ethyl.

Besides these, especially preferred compounds I.2 are those where Y_(n)is 6-methyl.

Particularly preferred with a view to their use are the compounds Iwhich are compiled in the tables which follow. In addition, the groupsmentioned in the tables for a substituent are an especially preferredembodiment of the substituent in question, independently of thecombination in which they are mentioned.

Table 1

Compounds of the formula I.1A where R^(a), R¹ and R² are methyl and thecombination of the radicals R³, R^(b) and R^(c) for a given compound ineach case corresponds to one line of Table A

Table 2

Compounds of the formula I.1A where R^(a) is methoxy, R¹ and R² aremethyl and the combination of the radicals R³, R^(b) and R^(c) for agiven compound in each case corresponds to one line of Table A

Table 3

Compounds of the formula I.2A where R^(a) and R¹ are methyl and thecombination of the radicals R², R³ and R^(d) for a given compound ineach case corresponds to one line of Table B

Table 4

Compounds of the formula I.2A where R^(a) is methoxy, R¹ is methyl andthe combination of the radicals R², R³ and R^(d) for a given compound ineach case corresponds to one line of Table B

Table 5

Compounds of the formula I.1B where R^(a), R¹ and R² are methyl and thecombination of the radicals R³, R^(b) and R^(c) for a given compound ineach case corresponds to one line of Table A

Table 6

Compounds of the formula I.1B where R^(a) is methoxy, R¹ and R² aremethyl and the combination of the radicals R³, R^(b) and R^(c) for agiven compound in each case corresponds to one line of Table A

Table 7

Compounds of the formula I.2B where R^(a) and R¹ are methyl and thecombination of the radicals R², R³ and R^(d) for a given compound ineach case corresponds to one line of Table B

Table 8

Compounds of the formula I.2B where R^(a) is methoxy, R¹ is methyl andthe combination of the radicals R², R³ and R^(d) for a given compound ineach case corresponds to one line of Table B

Table 9

Compounds of the formula I.1A where R^(a) and R² are methyl, R¹ is ethyland the combination of the radicals R³, R^(b) and R^(c) for a givencompound in each case corresponds to one line of Table A

Table 10

Compounds of the formula I.1A where R^(a) is methoxy, R¹ is ethyl and R²is methyl and the combination of the radicals R³, R^(b) and R^(c) for agiven compound in each case corresponds to one line of Table A

Table 11

Compounds of the formula I.2A where R^(a) and R¹ are ethyl and thecombination of the radicals R², R³ and R^(d) for a given compound ineach case corresponds to one line of Table B

Table 12

Compounds of the formula I.2A where R^(a) is methoxy and R¹ is ethyl andthe combination of the radicals R², R³ and R^(d) for a given compound ineach case corresponds to one line of Table B

Table 13

Compounds of the formula I.1B where R^(a) and R² are methyl, R¹ is ethyland the combination of the radicals R³, R^(b) and R^(c) for a givencompound in each case corresponds to one line of Table A

Table 14

Compounds of the formula I.1B where R^(a) is methoxy, R¹ is ethyl and R²is methyl and the combination of the radicals R³, R^(b) and R^(c) for agiven compound in each case corresponds to one line of Table A

Table 15

Compounds of the formula I.2B where R^(a) and R¹ are ethyl and thecombination of the radicals R², R³ and R^(d) for a given compound ineach case corresponds to one line of Table B

Table 16

Compounds of the formula I.2B where R^(a) is methoxy and R¹ is ethyl andthe combination of the radicals R², R³ and R^(d) for a given compound ineach case corresponds to one line of Table B

Table 17

Compounds of the formula I.1Ba where R^(a) is methoxy, R¹ and R² aremethyl and the combination of the radicals R³, R^(b) and R^(c) for agiven compound in each case corresponds to one line of Table A

Table 18

Compounds of the formula I.2Ba where R^(a) is methoxy and R¹ is methyland the combination of the radicals R², R³ and R^(d) for a givencompound in each case corresponds to one line of Table A

TABLE A No. R³ R^(b) R^(C) A-1 H H H A-2 H H CH₃ A-3 H H CH₂CH₃ A-4 H HCH₂CH₂CH₃ A-5 H H CH(CH₃)₂ A-6 H H C(CH₃)₃ A-7 H H CH₂C₆H₅ A-8 H HCH═CH—CH₃ A-9 H H C₆H₅ A-10 H H 4-Cl—C₆H₄ A-11 H H 4-F—C₆H₄ A-12 H CH₃CH₃ A-13 H CH₃ CH₂CH₃ A-14 H CH₃ CH₂CH₂CH₃ A-15 H CH₃ CH(CH₃)₂ A-16 HCH₃ C(CH₃)₃ A-17 H CH₃ CH₂C₆H₅ A-18 H CH₃ C₆H₅ A-19 H CH₃ 4-Cl—C₆H₄ A-20H CH₃ 4-F—C₆H₄ A-21 CH₃ H H A-22 CH₃ H CH₃ A-23 CH₃ H CH₂CH₃ A-24 CH₃ HCH₂CH₂CH₃ A-25 CH₃ H CH(CH₃)₂ A-26 CH₃ H C(CH₃)₃ A-27 CH₃ H CH₂C₆C₅ A-28CH₃ H CH═CH—CH₃ A-29 CH₃ H C₆H₅ A-30 CH₃ H 4-Cl—C₆H₄ A-31 CH₃ H 4-F—C₆H₄A-32 CH₃ CH₃ H A-33 CH₃ CH₃ CH₃ A-34 CH₃ CH₃ CH₂CH₃ A-35 H CH₃ H A-36 HCH₂CH₃ H A-37 H CH₂CH₂CH₃ H A-38 H CH(CH₃)₂ H A-39 H C(CH₃)₃ H A-40 HCH₂C₆C₅ H A-41 H CH═CH—CH₃ H A-42 H C₆H₅ H A-43 H 4-Cl—C₆H₄ H A-44 H4-F—C₆H₄ H A-45 H CH₂CH₃ CH₃ A-46 H CH₂CH₂CH₃ CH₃ A-47 H CH(CH₃)₂ CH₃A-48 H C(CH₃)₃ CH₃ A-49 H CH₂C₆C₅ CH₃ A-50 H C₆H₅ CH₃ A-51 H 4-Cl—C₆H₄CH₃ A-52 H 4-F—C₆H₄ CH₃ A-53 CH₃ CH₂CH₃ H A-54 CH₃ CH₂CH₂CH₃ H A-55 CH₃CH(CH₃)₂ H A-56 CH₃ C(CH₃)₃ H A-57 CH₃ CH₂C₆C₅ H A-58 CH₃ CH═CH—CH₃ HA-59 CH₃ C₆H₅ H A-60 CH₃ 4-CL—C₆H₄ H A-61 CH₃ 4-F—C₆H₄ H A-62 CH₃ CH₂CH₃CH₃

TABLE B No. R² R³ R^(d) B-1 CH₃ H CH₃ B-2 CH₃ H CH₂CH₃ B-3 CH₃ HCH₂CH₂CH₃ B-4 CH₃ H CH(CH₃)₂ B-5 CH₃ H C(CH₃)₃ B-6 CH₃ H CH₂CH═CH₂ B-7CH₃ H CH₂C≡CH B-8 CH₃ H CH₂CH₂CH₂CH₃ B-9 CH₃ CH₃ CH₃ B-10 CH₃ CH₃ CH₂CH₃B-11 CH₃ CH₃ CH₂CH₂CH₃ B-12 CH₃ CH₃ CH(CH₃)₂ B-13 CH₃ CH₃ C(CH₃)₃ B-14CH₃ CH₃ CH₂CH═CH₂ B-15 CH₃ CH₃ CH₂C≡CH B-16 CH₃ CH₃ CH₂CH₂CH₂CH₃ B-17CH₃ CH₂CH₃ CH₃ B-18 CH₃ CH₂CH₃ CH₂CH₃ B-19 CH₃ CH₂CH₃ CH₂CH₂CH₃ B-20 CH₃CH₂CH₃ CH(CH₃)₂ B-21 CH₃ CH₂CH₃ C(CH₃)₃ B-22 CH₃ CH₂CH₃ CH₂CH═CH₂ B-23CH₃ CH₂CH₃ CH₂C≡CH B-24 CH₃ CH₂CH₃ CH₂CH₂CH₂CH₃ B-25 CH₂CH₃ H CH₃ B-26CH₂CH₃ H CH₂CH₃ B-27 CH₂CH₃ H CH₂CH₂CH₃ B-28 CH₂CH₃ H CH(CH₃)₂ B-29CH₂CH₃ H C(CH₃)₃ B-30 CH₂CH₃ H CH₂CH═CH₂ B-31 CH₂CH₃ H CH₂C≡CH B-32CH₂CH₃ H CH₂CH₂CH₂CH₃ B-33 CH₂CH₃ CH₃ CH₃ B-34 CH₂CH₃ CH₃ CH₂CH₃ B-35CH₂CH₃ CH₃ CH₂CH₂CH₃ B-36 CH₂CH₃ CH₃ CH(CH₃)₂ B-37 CH₂CH₃ CH₃ C(CH₃)₃B-38 CH₂CH₃ CH₃ CH₂CH═CH₂ B-39 CH₂CH₃ CH₃ CH₂C≡CH B-40 CH₂CH₃ CH₃CH₂CH₂CH₂CH₃ B-41 CH₂CH₃ CH₂CH₃ CH₃ B-42 CH₂CH₃ CH₂CH₃ CH₂CH₃ B-43CH₂CH₃ CH₂CH₃ CH₂CH₂CH₃ B-44 CH₂CH₃ CH₂CH₃ CH(CH₃)₂ B-45 CH₂CH₃ CH₂CH₃C(CH₃)₃ B-46 CH₂CH₃ CH₂CH₃ CH₂CH═CH₂ B-47 CH₂CH₃ CH₂CH₃ CH₂C≡CH B-48CH₂CH₃ CH₂CH₃ CH₂CH₂CH₂CH₃

The compounds I are suitable as fungicides. They are distinguished by anoutstanding activity against a broad spectrum of phytopathogenic fungi,in particular from the classes of the Ascomycetes, Deuteromycetes,Phycomycetes and Basidiomycetes. Some of them act systemically, and theycan be employed in crop protection as foliar- and soil-actingfungicides.

They are especially important for controlling a large number of fungi ona variety of crop plants such as wheat, rye, barley, oats, rice, maize,grass, bananas, cotton, soya, coffee, sugar cane, grapevines, fruitspecies, ornamentals and vegetables such as cucumbers, beans, tomatoes,potatoes and cucurbits, and on the seeds of these plants.

Specifically, they are suitable for controlling the following plantdiseases:

Alternaria species on vegetables and fruit,

Botrytis cinerea (gray mold) on strawberries, vegetables, ornamentalsand grapevines,

Cercospora arachidicola on peanuts,

Erysiphe cichoracearum and Sphaerotheca fuliginea on cucurbits,

Erysiphe graminis (powdery mildew) on cereals,

Fusarium and Verticillium species on various plants,

Helminthosporium species on cereals,

Mycosphaerella species on bananas,

Phytophthora infestans on potatoes and tomatoes,

Plasmopara viticola on grapevines,

Podosphaera leucotricha on apples,

Pseudocercosporella herpotrichoides on wheat and barley,

Pseudocercosporella species on hops and cucumbers,

Puccinia species on cereals,

Pyricularia oryzae on rice,

Rhizoctonia species on cotton, rice and lawns,

Septoria nodorum on wheat,

Uncinula necator on grapevines,

Ustilago species on cereals and sugar cane, and

Venturia inaequalis (scab) on apples.

Moreover, the compounds I are suitable for controlling harmful fungisuch as Paecilomyces variotii in the protection of materials (eg. wood,paper, paint dispersions, fibers and woven tissues) and in theprotection of stored products.

The compounds I are applied by treating the fungi, or the plants, seeds,materials or the soil to be protected against fungal infection, with afungicidally active amount of the active ingredients. Application can beeffected both before and after infection of the materials, plants orseeds by the fungi.

In general, the fungicidal compositions comprise from 0.1 to 95,preferably 0.5 to 90, % by weight of active ingredient.

When used in crop protection, the rates of application are from 0.01 to2.0 kg of active ingredient per ha, depending on the nature of theeffect desired.

In the treatment of seed, amounts of active ingredient of from 0.001 to0.1 g, preferably 0.01 to 0.05 g, are generally required per kilogram ofseed.

When used in the protection of materials or stored products, the rate ofapplication of active ingredient depends on the nature of the field ofapplication and of the effect desired. Rates of applicationconventionally used in the protection of materials are, for example,from 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of active ingredientper cubic meter of material treated.

Moreover, the compounds of the formula I are suitable for efficientlycontrolling animal pests from the classes of the insects, arachnids andnematodes. They can be employed in crop protection and in the hygiene,stored-product and veterinary sector for controlling animal pests. Inparticular, they are suitable for controlling the following animalpests:

insects from the order of the lepidopterans (Lepidoptera), eg. Agrotisypsilon, Agrotis segetum, Alabama argillacea, Anticarsia gemmatalis,Argyresthia conjugella, Autographa gamma, Bupalus piniarius, Cacoeciamurinana, Capua reticulana, Cheimatobia brumata, Choristoneurafumiferana, Choristoneura occidentalis, Cirphis unipuncta, Cydiapomonella, Dendrolimus pini, Diaphania nitidalis, Diatraea grandiosella,Earias insulana, Elasmopalpus lignosellus, Eupoecilia ambiguella,Evetria bouliana, Feltia subterranea, Galleria mellonella, Grapholithafunebrana, Grapholitha molesta, Heliothis armigera, Heliothis virescens,Heliothis zea, Hellula undalis, Hibernia defoliaria, Hyphantria cunea,Hyponomeuta malinellus, Keiferia lycopersicella, Lambdina fiscellaria,Laphygma exigua, Leucoptera coffeella, Leucoptera scitella,Lithocolletis blancardella, Lobesia botrana, Loxostege sticticalis,Lymantria dispar, Lymantria monacha, Lyonetia clerkella, Malacosomaneustria, Mamestra brassicae, Orgyia pseudotsugata, Ostrinia nubilalis,Panolis flammea, Pectinophora gossypiella, Peridroma saucia, Phalerabucephala, Phthorimaea operculella, Phyllocnistis citrella, Pierisbrassicae, Plathypena scabra, Plutella xylostella, Pseudoplusiaincludens, Rhyacionia frustrana, Scrobipalpula absoluta, Sitotrogacerealella, Sparganothis pilleriana, Spodoptera frugiperda, Spodopteralittoralis, Spodoptera litura, Thaumatopoea pityocampa, Tortrixviridana, Trichoplusia ni and Zeiraphera canadensis,

beetles (Coleoptera), eg. Agrilus sinuatus, Agriotes lineatus, Agriotesobscurus, Amphimallus solstitialis, Anisandrus dispar, Anthonomusgrandis, Anthonomus pomorum, Atomaria linearis, Blastophagus piniperda,Blitophaga undata, Bruchus rufimanus, Bruchus pisorum, Bruchus lentis,Byctiscus betulae, Cassida nebulosa, Cerotoma trifurcata,Ceuthorrhynchus assimilis, Ceuthorrhynchus napi, Chaetocnema tibialis,Conoderus vespertinus, Crioceris asparagi, Diabrotica longicornis,Diabrotica 12-punctata, Diabrotica virgifera, Epilachna varivestis,Epitrix hirtipennis, Eutinobothrus brasiliensis, Hylobius abietis,Hypera brunneipennis, Hypera postica, Ips typographus, Lema bilineata,Lema melanopus, Leptinotarsa decemlineata, Limonius californicus,Lissorhoptrus oryzophilus, Melanotus communis, Meligethes aeneus,Melolontha hippocastani, Melolontha melolontha, Oulema oryzae,Ortiorrhynchus sulcatus, Otiorrhynchus ovatus, Phaedon cochleariae,Phyllotreta chrysocephala, Phyllophaga sp., Phyllopertha horticola,Phyllotreta nemorum, Phyllotreta striolata, Popillia japonica, Sitonalineatus and Sitophilus granaria,

dipterans (Diptera), eg. Aedes aegypti, Aedes vexans, Anastrepha ludens,Anopheles maculipennis, Ceratitis capitata, Chrysomya bezziana,Chrysomya hominivorax, Chrysomya macellaria, Contarinia sorghicola,Cordylobia anthropophaga, Culex pipiens, Dacus cucurbitae, Dacus oleae,Dasineura brassicae, Fannia canicularis, Gasterophilus intestinalis,Glossina morsitans, Haematobia irritans, Haplodiplosis equestris,Hylemyia platura, Hypoderma lineata, Liriomyza sativae, Liriomyzatrifolii, Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lycoriapectoralis, Mayetiola destructor, Musca domestica, Muscina stabulans,Oestrus ovis, Oscinella frit, Pegomya hysocyami, Phorbia antiqua,Phorbia brassicae, Phorbia coarctata, Rhagoletis cerasi, Rhagoletispomonella, Tabanus bovinus, Tipula oleracea and Tipula paludosa,

thrips (Thysanoptera), eg. Frankliniella fusca, Frankliniellaoccidentalis, Frankliniella tritici, Scirtothrips citri, Thrips oryzae,Thrips palmi and Thrips tabaci,

hymenopterans (Hymenoptera), eg. Athalia rosae, Atta cephalotes, Attasexdens, Atta texana, Hoplocampa minuta, Hoplocampa testudinea,Monomorium pharaonis, Solenopsis geminata and Solenopsis invicta,

heteropterans (Heteroptera), eg. Acrosternum hilare, Blissusleucopterus, Cyrtopeltis notatus, Dysdercus cingulatus, Dysdercusintermedius, Eurygaster integriceps, Euschistus impictiventris,Leptoglossus phyllopus, Lygus lineolaris, Lygus pratensis, Nezaraviridula, Piesma quadrata, Solubea insularis and Thyanta perditor,

homopterans (Homoptera), eg. Acyrthosiphon onobrychis, Adelges laricis,Aphidula nasturtii, Aphis fabae, Aphis pomi, Aphis sambuci, Brachycauduscardui, Brevicoryne brassicae, Cerosipha gossypii, Dreyfusianordmannianae, Dreyfusia piceae, Dysaphis radicola, Dysaulacorthumpseudosolani, Empoasca fabae, Macrosiphum avenae, Macrosiphumeuphorbiae, Macrosiphon rosae, Megoura viciae, Metopolophium dirhodum,Myzodes persicae, Myzus cerasi, Nilaparvata lugens, Pemphigus bursarius,Perkinsiella saccharicida, Phorodon humuli, Psylla mali, Psylla piri,Rhopalomyzus ascalonicus, Rhopalosiphum maidis, Sappaphis mala,Sappaphis mali, Schizaphis graminum, Schizoneura lanuginosa,Trialeurodes vaporariorum and Viteus vitifolii,

termites (Isoptera), eg. Calotermes flavicollis, Leucotermes flavipes,Reticulitermes lucifugus and Termes natalensis,

orthopterans (Orthoptera), eg. Acheta domestica, Blatta orientalis,Blattella germanica, Forficula auricularia, Gryllotalpa gryllotalpa,Locusta migratoria, Melanoplus bivittatus, Melanoplus femur-rubrum,Melanoplus mexicanus, Melanoplus sanguinipes, Melanoplus spretus,Nomadacris septemfasciata, Periplaneta americana, Schistocercaamericana, Schistocerca peregrina, Stauronotus maroccanus and Tachycinesasynamorus,

Arachnoidea, such as arachnids (Acarina), eg. Amblyomma americanum,Amblyomma variegatum, Argas persicus, Boophilus annulatus, Boophilusdecoloratus, Boophilus microplus, Brevipalpus phoenicis, Bryobiapraetiosa, Dermacentor silvarum, Eotetranychus carpini, Eriophyessheldoni, Hyalomma truncatum, Ixodes ricinus, Ixodes rubicundus,Ornithodorus moubata, Otobius megnini, Paratetranychus pilosus,Dermanyssus gallinae, Phyllocoptruta oleivora, Polyphagotarsonemuslatus, Psoroptes ovis, Rhipicephalus appendiculatus, Rhipicephalusevertsi, Sarcoptes scabiei, Tetranychus cinnabarinus, Tetranychuskanzawai, Tetranychus pacificus, Tetranychus telarius and Tetranychusurticae,

nematodes such as root knot nematodes, eg. Meloidogyne hapla,Meloidogyne incognita, Meloidogyne javanica, cyst-forming nematodes, eg.Globodera rostochiensis, Heterodera avenae, Heterodera glycines,Heterodera schachtii, Heterodera trifolii, stem eelworms and foliarnematodes, eg. Belonolaimus longicaudatus, Ditylenchus destructor,Ditylenchus dipsaci, Heliocotylenchus multicinctus, Longidoruselongatus, Radopholus similis, Rotylenchus robustus, Trichodorusprimitivus, Tylenchorhynchus claytoni, Tylenchorhynchus dubius,Pratylenchus neglectus, Pratylenchus penetrans, Pratylenchus curvitatusand Pratylenchus goodeyi.

The rate of application of active ingredient for controlling animalpests is from 0.1 to 2.0, preferably 0.2 to 1.0, kg/ha under fieldconditions.

The compounds I can be converted into the customary formulations, eg.solutions, emulsions, suspensions, dusts, powders, pastes and granules.The use form depends on the particular purpose; in any case, it shouldguarantee a fine and uniform distribution of the compound according tothe invention.

The formulations are prepared in a known manner, eg. by extending theactive ingredient with solvents and/or carriers, if desired usingemulsifiers and dispersants, it also being possible to use other organicsolvents as auxiliary solvents if water is used as the diluent.Auxiliaries which are suitable are essentially: solvents such asaromatics (eg. xylene), chlorinated aromatics (eg. chlorobenzenes),paraffins (eg. mineral oil fractions), alcohols (eg. methanol, butanol),ketones (eg. cyclohexanone), amines (eg. ethanolamine,dimethylformamide) and water; carriers such as ground natural minerals(eg. kaolins, clays, talc, chalk) and ground synthetic minerals (eg.highly-disperse silica, silicates); emulsifiers such as non-ionic andanionic emulsifiers (eg. polyoxyethylene fatty alcohol ethers,alkylsulfonates and arylsulfonates) and dispersants such aslignin-sulfite waste liquors and methylcellulose.

Suitable surfactants are alkali metal, alkaline earth metal and ammoniumsalts of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonicacid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkylsulfates, alkylsulfonates, fatty alcohol sulfates and fatty acids andtheir alkali metal and alkaline earth metal salts, salts of sulfatedfatty alcohol glycol ether, condensates of sulfonated naphthalene andnaphthalene derivatives with formaldehyde, condensates of naphthalene orof napthalenesulfonic acid with phenol and formaldehyde, polyoxyethyleneoctylphenyl ether, ethoxylated isooctylphenol, octylphenol, nonylphenol,alkylphenyl polyglycol ethers, tributylphenyl polyglycol ether,alkylaryl polyether alcohols, isotridecyl alcohol, fattyalcohol/ethylene oxide condensates, ethoxylated castor oil,polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, laurylalcohol polyglycol ether acetal, sorbitol esters, lignin-sulfite wasteliquors and methylcellulose.

Substances which are suitable for the preparation of directly sprayablesolutions, emulsions, pastes or oil dispersions are mineral oilfractions of medium to high boiling point, such as kerosene or dieseloil, furthermore coal tar oils and oils of vegetable or animal origin,aliphatic, cyclic and aromatic hydrocarbons, eg. benzene, toluene,xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or theirderivatives, methanol, ethanol, propanol, butanol, chloroform, carbontetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isophorone,strongly polar solvents, eg. dimethylformamide, dimethyl sulfoxide,N-methylpyrrolidone and water.

Powders, materials for spreading and dusts can be prepared by mixing orconcomitantly grinding the active substances with a solid carrier.

Granules, eg. coated granules, impregnated granules and homogeneousgranules, can be prepared by binding the active ingredients to solidcarriers. Examples of solid carriers are mineral earths, such assilicas, silica gels, silicates, talc, kaolin, attaclay, limestone,lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calciumsulfate, magnesium sulfate, magnesium oxide, ground synthetic materials,fertilizers, eg. ammonium sulfate, ammonium phosphate, ammonium nitrate,ureas, and products of vegetable origin, such as cereal meal, tree barkmeal, wood meal and nutshell meal, cellulose powders and other solidcarriers.

In general, the formulations comprise from 0.01 to 95% by weight,preferably from 0.1 to 90% by weight, of the active ingredient. Theactive ingredients are employed in a purity of from 90% to 100%,preferably 95% to 100% (according to NMR spectrum).

The following are exemplary formulations:

I. 5 parts by weight of a compound according to the invention are mixedintimately with 95 parts by weight of finely divided kaolin. This givesa dust which comprises 5% by weight of the active ingredient.

II. 30 parts by weight of a compound according to the invention aremixed intimately with a mixture of 92 parts by weight of pulverulentsilica gel and 8 parts by weight of paraffin oil which had been sprayedonto the surface of this silica gel. This gives a formulation of theactive ingredient with good adhesion properties (comprises 23% by weightof active ingredient).

III. 10 parts by weight of a compound according to the invention aredissolved in a mixture composed of 90 parts by weight of xylene, 6 partsby weight of the adduct of 8 to 10 mol of ethylene oxide and 1 mol ofoleic acid N-monoethanolamide, 2 parts by weight of calciumdodecylbenzenesulfonate and 2 parts by weight of the adduct of 40 mol ofethylene oxide and 1 mol of castor oil (comprises 9% by weight of activeingredient).

IV. 20 parts by weight of a compound according to the invention aredissolved in a mixture composed of 60 parts by weight of cyclohexanone,30 parts by weight of isobutanol, 5 parts by weight of the adduct of 7mol of ethylene oxide and 1 mol of isooctylphenol and 5 parts by weightof the adduct of 40 mol of ethylene oxide and 1 mol of castor oil(comprises 16% by weight of active ingredient).

V. 80 parts by weight of a compound according to the invention are mixedthoroughly with 3 parts by weight of sodiumdiisobutylnaphthalene-alpha-sulfonate, 10 parts by weight of the sodiumsalt of a lignosulfonic acid from a sulfite waste liquor and 7 parts byweight of pulverulent silica gel, and the mixture is ground in a hammermill (comprises 80% by weight of active ingredient).

VI. 90 parts by weight of a compound according to the invention aremixed with 10 parts by weight of N-methyl-α-pyrrolidone, which gives asolution which is suitable for use in the form of microdrops (comprises90% by weight of active ingredient).

VII. 20 parts by weight of a compound according to the invention aredissolved in a mixture composed of 40 parts by weight of cyclohexanone,30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7mol of ethylene oxide and 1 mol of isooctylphenol and 10 parts by weightof the adduct of 40 mol of ethylene oxide and 1 mol of castor oil.Pouring the solution into 100,000 parts by weight of water and finelydistributing it therein gives an aqueous dispersion which comprises0.02% by weight of active ingredient.

VIII. 20 parts by weight of a compound according to the invention aremixed thoroughly with 3 parts by weight of sodiumdiisobutylnaphthalene-α-sulfonate, 17 parts by weight of the sodium saltof a lignosulfonic acid from a sulfite waste liquor and 60 parts byweight of pulverulent silica gel, and the mixture is ground in a hammermill. Finely distributing the mixture in 20,000 parts by weight of watergives a spray mixture which comprises 0.1% by weight of activeingredient.

The active ingredients can be used as such, in the form of theirformulations or the use forms prepared therefrom, eg. in the form ofdirectly sprayable solutions, powders, suspensions or dispersions,emulsions, oil dispersions, pastes, dusts, materials for spreading, orgranules, by means of spraying, atomizing, dusting, spreading orpouring. The use forms depend entirely on the intended purposes; in anycase, this is intended to guarantee the finest possible distribution ofthe active ingredients according to the invention.

Aqueous use forms can be prepared from emulsion concentrates, pastes orwettable powders (sprayable powders, oil dispersions) by adding water.To prepare emulsions, pastes or oil dispersions, the substances as suchor dissolved in an oil or solvent, can be homogenized in water by meansof wetter, tackifier, dispersant or emulsifier. Alternatively, it ispossible to prepare concentrates composed of active substance, wetter,tackifier, dispersant or emulsifier and, if appropriate, solvent or oil,which concentrates are suitable for dilution with water.

The active ingredient concentrations in the ready-to-use products can bevaried within substantial ranges. In general, they are from 0.0001 to10%, preferably from 0.01 to 1%.

The active ingredients may also be used successfully in theultra-low-volume process (ULV), it being possible to apply formulationscomprising over 95% by weight of active ingredient, or even the activeingredient without additives.

Various types of oils, herbicides, fungicides, other pesticides, orbactericides may be added to the active ingredients, if appropriate alsoonly immediately prior to use (tank mix). These agents can be admixedwith the agents according to the invention in a weight ratio of 1:10 to10:1.

In the use form as fungicides, the compositions according to theinvention can also be present together with other active ingredients,eg. with herbicides, insecticides, growth regulators, fungicides or elsewith fertilizers. Mixing the compounds I or the compositions comprisingthem in the use form as fungicides with other fungicides frequentlyresults in a broader fungicidal spectrum of action.

The following list of fungicides together with which the compoundsaccording to the invention can be used is intended to illustrate thepossible combinations, but not to impose any limitation:

sulfur, dithiocarbamates and their derivatives, such as iron(III)dimethyldithiocarbamate, zinc dimethyldithiocarbamate, zincethylenebisdithiocarbamate, manganese ethylenebisdithiocarbamate,manganese zinc ethylenediaminebisdithiocarbamate, tetramethylthiuramdisulfide, ammonia complex of zinc (N,N-ethylenebisdithiocarbamate),ammonia complex of zinc (N,N′-propylenebisdithiocarbamate), zinc(N,N′-propylenebisdithiocarbamate),N,N′-polypropylenebis(thiocarbamoyl)disulfide;

nitro derivatives, such as dinitro(1-methylheptyl)phenyl crotonate,2-sec-butyl-4,6-dinitrophenyl 3,3-dimethylacrylate,2-sec-butyl-4,6-dinitrophenylisopropyl carbonate, diisopropyl5-nitro-isophthalate;

heterocyclic substances, such as 2-heptadecyl-2-imidazoline acetate,2,4-dichloro-6-(o-chloroanilino)-s-triazine, O,O-diethylphthalimidophosphonothioate,5-amino-1-[bis-(dimethylamino)phosphinyl]-3-phenyl-1,2,4-triazole,2,3-dicyano-1,4-dithioanthraquinone, 2-thio-1,3-dithiolo[4,5-b]quinoxaline, methyl 1-(butylcarbamoyl)-2-benzimidazolecarbamate,2-methoxycarbonylaminobenzimidazole, 2-(2-furyl)benzimidazole,2-(4-thiazolyl)benzimidazole,N-(1,1,2,2-tetrachloroethylthio)tetrahydrophthalimide,N-trichloromethylthio-tetrahydrophthalimide,N-trichloromethylthiophthalimide,

N-dichlorofluoromethylthio-N′,N′-dimethyl-N-phenylsulfodiamide,5-ethoxy-3-trichloromethyl-1,2,3-thiadiazole,2-thiocyanatomethylthiobenzothiazole, 1,4-dichloro-2,5-dimethoxybenzene,4-(2-chlorophenylhydrazono)-3-methyl-5-isoxazolone, pyridine-2-thiol1-oxide, 8-hydroxyquinoline or its copper salt,2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiine,2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiine 4,4-dioxide,2-methyl-5,6-dihydro-4H-pyran-3-carboxanilide,2-methylfuran-3-carboxanilide, 2,5-dimethylfuran-3-carboxanilide,2,4,5-trimethylfuran-3-carboxanilide,N-cyclohexyl-2,5-dimethylfuran-3-carboxamide,N-cyclohexyl-N-methoxy-2,5-dimethylfuran-3-carboxamide,2-methylbenzanilide, 2-iodobenzanilide,N-formyl-N-morpholine-2,2,2-trichloroethyl acetal,piperazine-1,4-diylbis-1-(2,2,2-trichloroethyl)formamide,1-(3,4-dichloroanilino)-1-formylamino-2,2,2-trichlorethane;

amines such as 2,6-dimethyl-N-tridecylmorpholine or its salts,2,6-dimethyl-N-cyclododecylmorpholine or its salts,N-[3-(p-tert-butylphenyl)-2-methylpropyl]-cis-2,6-dimethylmorpholine,N-[3-(p-tert-butylphenyl)-2-methylpropyl]piperidine,(8-(1,1-dimethylethyl)-N-ethyl-N-propyl-1,4-dioxaspiro[4.5]decane-2-methanamine;

azoles such as1-[2-(2,4-dichlorophenyl)-4-ethyl-1,3-dioxolan-2-yl-ethyl]-1H-1,2,4-triazole,1-[2-(2,4-dichlorophenyl)-4-n-propyl-1,3-dioxolan-2-yl-ethyl]-1H-1,2,4-triazole,N-(n-propyl)-N-(2,4,6-trichlorophenoxyethyl)-N′-imidazolyl-urea,1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)-2-butanone,1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)-2-butanol,(2RS,3RS)-1-[3-(2-chlorophenyl)-2-(4-fluorophenyl)oxiran-2-ylmethyl]-1H-1,2,4-triazole,1-[2-(2,4-dichlorophenyl)pentyl]-1H-1,2,4-triazole,2,4′-difluoro-α-(1H-1,2,4-triazolyl-1-methyl)benzhydryl alcohol,1-((bis-(4-fluorophenyl)methylsilyl)methyl)-1H-1,2,4-triazole,1-[2RS,4RS;2RS,4SR)-4-bromo-2-(2,4-dichlorophenyl)tetrahydrofuryl]-1H-1,2,4-triazole,2-(4-chlorophenyl)-3-cyclopropyl-1-(1H-1,2,4-triazol-1-yl)butan-2-ol,(+)-4-chloro-4-[4-methyl-2-(1H-1,2,4-triazol-1-yl-methyl)-1,3-dioxolan-2-yl]-phenyl-4-chlorophenylether,(E)-(R,S)-1-(2,4-dichlorophenyl)-4,4-dimethyl-2-(1H-1,2,-4-triazol-1-yl)pent-1-en-3-ol,4-(4-chlorophenyl)-2-phenyl-2-(1H-1,2,4-triazolylmethyl)butyronitrile,3-(2,4-dichlorophenyl)-6-fluoro-2-(1H-1,2,4-triazol-1-yl)quinazolin-4(3H)-one,(R,S)-2-(2,4-dichlorophenyl)-1H-1,2,4-triazol-1-yl)hexan-2-ol,(1RS,5RS;1RS,5SR)-5-(4-chlorobenzyl)-2,2-dimethyl-1-(1H-1,2,4-triazol-1-ylmethyl)cyclopentanol,(R,S)-1-(4-chlorophenyl)-4,4-dimethyl-3-(1H-1,2,4-triazol-1-ylmethyl)pentan-3-ol,(+)-2-(2,4-dichlorophenyl)-3-(1H-1,2,4-triazolyl)propyl-1,1,2,2-tetrafluoroethylether,(E)-1-[1-[4-chloro-2-trifluoromethyl)phenyl]imino)-2-propoxyethyl]-1H-imidazole,2-(4-chlorophenyl)-2-(1H-1,2,4-triazol-1-ylmethyl)hexanonitrile;

α-(2-chlorophenyl)-α-(4-chlorophenyl)-5-pyrimidinemethanol,5-butyl-2-dimethylamino-4-hydroxy-6-methylpyrimidine,bis(p-chlorophenyl)-3-pyridinemethanol,1,2-bis(3-ethoxycarbonyl-2-thioureido)benzene,1,2-bis(3-methoxycarbonyl-2-thioureido)benzene,

strobilurins such as methylE-methoxyimino-[α-(o-tolyloxy)-o-tolyl]acetate, methylE-2-{2-[6-(2-cyanophenoxy)pyrimidin-4-yloxy]-phenyl}-3-methoxyacrylate,N-methyl-E-methoxyimino-[α-(2-phenoxyphenyl)]-acetamide, methylE-methoxyimino-[α-(2,5-dimethylphenoxy)-o-tolyl]acetamide,

anilinopyrimidines such as N-(4,6-dimethylpyrimidin-2-yl)aniline,N-[4-methyl-6-(1-propynyl)pyrimidin-2-yl]aniline,N-[4-methyl-6-cyclopropylpyrimidin-2-yl]aniline,

phenylpyrroles such as4-(2,2-difluoro-1,3-benzodioxol-4-yl)pyrrole-3-carbonitrile,

cinnamamides such as3-(4-chlorophenyl)-3-(3,4-dimethoxyphenyl)acryloylmorpholine,

and a variety of fungicides such as dodecylguanidine acetate,3-[3-(3,5-dimethyl-2-oxycyclohexyl)-2-hydroxyethyl]glutarimide,N-methyl-N-ethyl-(4-trifluoromethyl-2-[3′,4′-dimethoxyphenyl]-benzamide,hexachlorobenzene, methylN-(2,6-dimethylphenyl)-N-(2-furoyl)-DL-alaninate,DL-N-(2,6-dimethylphenyl)-N-(2′-methoxyacetyl)alanine methyl ester,N-(2,6-dimethylphenyl)-N-chloroacetyl-D,L-2-aminobutyrolactone,DL-N-(2,6-dimethylphenyl)-N-(phenylacetyl)alanine methyl ester,5-methyl-5-vinyl-3-(3,5-dichlorophenyl)-2,4-dioxo-1,3-oxazolidine,3-(3,5-dichlorophenyl)5-methyl-5-methoxymethyl-1,3-oxazolidine-2,4-dione,3-(3,5-dichlorophenyl)-1-isopropylcarbamoylhydantoin,N-(3,5-dichlorophenyl)-1,2-dimethylcyclopropane-1,2-dicarboximide,2-cyano-[N-(ethylaminocarbonyl)-2-methoximino]acetamide,N-(3-chloro-2,6-dinitro-4-trifluoromethylphenyl)-5-trifluoromethyl-3-chloro-2-aminopyridine.

SYNTHESIS EXAMPLES

With due modification of the starting compounds, the protocols shown inthe synthesis examples below were used for obtaining further compoundsI. The resulting compounds, together with physical data, are listed inthe Tables which follow.

Example 1 Preparation of

Method A:

A solution of 1.1 g of4-[(2-bromomethyl)phenyl]-2,4-dihydro-5-methoxy-2-methyl-3H-1,2,4-triazol-3-one[cf. WO-A 97/00,612], 1.35 g of potassium carbonate and 0.68 g of2,3,4-pentanetrione 2-(E)-3-(Z)-bis(O-methyloxime)-4-(E)-oxime (cf. DE-A195 39 324] in 35 ml of dimethylformamide (DMF) was stirred at 25-35° C.for 8 h. The reaction mixture was then poured onto ice-water andextracted with methyl tert-butyl ether and the combined organic phaseswere washed with sat. ammonium chloride solution and dried. The solventwas distilled off and the residue was subjected to silica gelchromatography (cyclohexane/ethyl acetate 80:20), giving 400 mg ofproduct as a clear powder of mp. 142-145° C.

IR (cm−1): 1715, 1611, 1502, 1481, 1415, 1049, 999, 988, 895.

Method B:

1.1 g of4-[(2-bromomethyl)phenyl]-2,4-dihydro-5-chloro-2-methyl-3H-1,2,4-triazol-3-one[cf. WO-A 97/19935, Table B, p. 23, comp. No. 77], dissolved in 15 ml ofDMF, were stirred with 1.35 g of potassium carbonate and 0.68 g of2,3,4-pentanetrione 2-(E)-3-(Z)-bis(O-methyloxime)-4-(E)-oxime [cf. DE-A195 39 324] at 22-25° C. for approximately 12 h. The reaction mixturewas then poured onto ice-water and extracted with methyl tert-butylether and the combined organic phases were washed with sat. ammoniumchloride solution and dried. The solvent was distilled off and theresidue was subjected to silica gel chromatography (cyclohexane/ethylacetate 80:20). The crude product (700 mg) was dissolved in 5 ml ofdimethoxyethane and 5 ml of methanol and admixed with 0.61 g of a 30%strength methanolic sodium methoxide solution. The reaction mixture washeated under reflux for approximately 20 h, taken up in methylenechloride, washed with water and sat. ammonium chloride solution and thendried. The solvent was distilled off and the residue was subjected tosilica gel chromatography (cyclohexane/ethyl acetate 80:20), giving 300mg of the title compound as a clear powder of mp. 142-145° C.

IR (cm−1): 1715, 1611, 1502, 1481, 1415, 1049, 999, 988, 895.

TABLE I I

Phys. data (mp. No. X Y_(n) R¹ R² R³ R⁴ [° C.]) I-1 B H CH₃ CH₃ H═C(CH₃)₂ 92-95 (R^(a) = OCH₃) I-2 B H CH₃ CH₃ CH₃ ═NOCH₃ 142-145 (R^(a)= OCH₃)

Examples of the Action Against Harmful Fungi

The fungicidal action of the compounds of the formula I was demonstratedby the following experiments:

The active ingredients were formulated separately or jointly as a 10%emulsion in a mixture of 70% by weight of cyclohexanone, 20% by weightof Nekanil® LN (Lutensol® AP6, wetter with emulsifying and dispersingaction based on ethoxylated alkylphenols) and 10% by weight of Wettol®EM (non-ionic emulsifier based on ethoxylated castor oil) and dilutedwith water to suit the desired concentration.

Use Example 1—Activity Against Powdery Mildew of Wheat

Leaves of potted wheat seedlings c.v. “Frühgold” were sprayed to runoffpoint with an aqueous preparation of active ingredient made from a stocksolution comprising 10% of active ingredient, 63% of cyclohexanone and27% of emulsifier, and, 24 hours after the spray coating had dried on,dusted with spores of powdery mildew of wheat (Erysiphe graminis formaspecialis tritici). The test plants were subsequently kept in agreenhouse at from 20 to 24° C. and from 60 to 90% relative atmospherichumidity. After 7 days, the extent of the mildew development wasdetermined visually as % infection of the total leaf area.

Use Example 2—Activity Against Pyricularia oryzae (Protective)

Leaves of potted rice seedlings c.v. “Tai-Nong 67” were sprayed torunoff point with an aqueous preparation of active ingredient made froma stock solution comprising 10% of active ingredient, 63% ofcyclohexanone and 27% of emulsifier. The following day, the plants wereinoculated with an aqueous spore suspension of Pyricularia oryzae. Thetest plants were subsequently kept in climatized chambers at 22-24° C.and 95-99% relative atmospheric humidity for 6 days. The extent of thedevelopment of the infection on the leaves was then determined visually.

In these tests, the plants which had been treated with 16 ppm of thecompound No. I-1 of Table I showed at most 5% infection, whereas theuntreated plants were infected to 80 or 85%.

Examples of the Action Against Animal Pests

The action of the compounds of the formula I against animal pests wasdemonstrated by the following experiments:

The active ingredients were formulated

a. as a 0.1% strength solution in acetone or

b. as a 10% emulsion in a mixture of 70% by weight of cyclohexanone, 20%by weight of Nekanil® LN (Lutensol® AP6, wetter with emulsifying anddispersing action based on ethoxylated alkylphenols) and 10% by weightof Wettol® EM (non-ionic emulsifier based on ethoxylated castor oil)

and diluted to give the desired concentration, using acetone in the caseof a. and water in the case of b.

After the experiments had been concluded, in each case the lowestconcentration was determined at which the compounds still caused an 80to 100% inhibition or mortality in comparison with untreated controls(limit or minimal concentration).

We claim:
 1. A bisimino-substituted phenyl compound of formula I

wherein X is a group A or B

 where # denotes the bond with the phenyl ring and R^(a) is halogen, C₁-C₄-alkyl or C₁-C₄-alkoxy; Y is halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl or C₁-C₄-alkoxy; n is 0, 1 or 2, wherein the radicals Y are identical or different when n is 2; R¹ is C₁-C₄-alkyl; R² is C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₃-C₄-alkenyl, C₃-C₄-haloalkenyl, C₃-C₄-alkynyl or C₃-C₄-haloalkynyl; R³ is hydrogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl or substituted or unsubstituted phenyl; R⁴ is ═CR^(b)R^(c) or ═N—OR^(d) where R^(b), R^(c) independently of one another are hydrogen, C₁-C₆-alkyl or substituted or unsubstituted phenyl; R^(d) is C₁-C₄-alkyl, C₁₋₄-haloalkyl, C₃-C₄-alkenyl, C₃-C₄-haloalkenyl, C₃-C₄-alkynyl or C₃-C₄-haloalkynyl; and wherein the phenyl radical represented by R³, R^(b) or R^(c) is unsubstituted or is partially or fully halogenated, or carries, optionally in addition to the halogen substituents, one to four radicals selected from the group consisting of: cyano, nitro, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylamino, di-C₁-C₄-alkylamino and C₁-C₄-alkylthio.
 2. A process for the preparation of the compound of formula I defined in claim 1 wherein R⁴ denotes the CR^(b)R^(c) group, which comprises reacting a benzyl compound of formula II

where L is a nucleophilically exchangeable group with an oxime of formula III

and converting the resulting oxime ether of formula IV

into a halogen compound of formula V

by means of halogenation, reacting V with a hydroxylamine ether of formula VI′ H₂N—OR²  VI′ to give a bisoxime of formula VI,

oxidizing VI to give a carbonyl compound of formula VII

and reacting VII with a phosphorus reagent following the principles of a wittig reaction.
 3. A process for the preparation of the compound of formula I defined in claim 1 wherein R⁴ denotes the NOR^(d) group, which comprises reacting a carbonyl compound of formula VII

with a hydroxylamine ether of formula VIII H₂N—OR^(d)  VII.
 4. A carbonyl compound of formula VII

wherein X is a group A or B

 where # denotes the bond with the phenyl ring and R^(a) is halogen, C₁-C₄-alkyl or C₁-C₄-alkoxy; Y is halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl or C₁-C₄-alkoxy; n is 0, 1 or 2, wherein the radicals Y are identical or different when n is 2; R¹ is C₁-C₄-alkyl; R² is C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₃-C₄-alkenyl, C₃C₄-haloalkenyl, C₃-C₄-alkynyl or C₃-C₄-haloalkynyl; R³ is hydrogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl or phenyl which is unsubstituted or is partially or fully halogenated, or carries, optionally in addition to the halogen substituents, one to four radicals selected from the group consisting of: cyano, nitro, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylamino, di-C₁-C₄-alkylamino and C₁-C₄-alkylthio.
 5. A composition which is suitable for controlling animal pests or harmful fungi, comprising a solid or liquid carrier and the compound of formula I defined in claim
 1. 6. A method of controlling harmful fungi, which comprises treating the fungi, or materials, plants, soil or seeds to be protected against fungal infection, with an effective amount of the compound of formula I defined in claim
 1. 7. A method of controlling animal pests, which comprises treating the animal pests, or materials, plants, soil or seeds to be protected against said pests, with an effective amount of the compound of formula I defined in claim
 1. 8. The compound of formula I defined in claim 1, wherein the phenyl radical represented by R³, R^(b) or R^(c) is unsubstituted or is partially or fully halogenated, or carries, optionally in addition to the halogen substituents, one to four radicals selected from the group consisting of: cyano, nitro, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylamino, di-C₁-C₄-alkylamino and C₁-C₄-alkylthio.
 9. A compound of formula I defined in claim 1, wherein R^(a) represents a C₁-C₂-alkyl or a C₁-C₂-alkoxy group.
 10. The compound of formula I defined in claim 1, wherein R^(a) represents methyl or methoxy.
 11. The compound of formula I defined in claim 1, wherein n is
 0. 12. The compound of formula I defined in claim 1, wherein X represents the group B.
 13. The compound of formula I defined in claim 1, wherein R⁴ represents the CR^(b)R^(c) group.
 14. The compound of formula I defined in claim 13, wherein R^(b) denotes hydrogen.
 15. The compound of formula I defined in claim 13, wherein R² is methyl or ethyl, and Y_(n) represents hydrogen or a 6-methyl group.
 16. The compound of formula I defined in claim 1, wherein R⁴ represents the NOR^(d) group.
 17. The compound of formula I defined in claim 16, wherein R¹ and R³ are methyl, Y_(n) represents hydrogen, and R² is methyl or ethyl.
 18. The compound of formula I defined in claim 16, wherein Y_(n) represents a 6-methyl group.
 19. The process of claim 2, wherein the nucleophilically exchangeable group L denotes halogen, or an alkyl or aryl sulfonate.
 20. The process of claim 2, wherein the nucleophilically exchangeable group L denotes chlorine, bromine, methylsylate or tosylate. 